Process for the synthesis of amine ethers from secondary amino oxides

ABSTRACT

Amine ethers of sterically hindered amines are obtained in good yield from the corresponding N-oxyl hindered amine precursor by reaction with a hydrocarbon in the presence of an organic hydroperoxide and an iodide. The products of present process find utility as polymerization regulators and/or light stabilizers for organic material.

The instant invention pertains to a process for preparing amine ethers,e.g. N-hydrocarbyloxy substituted hindered amine compounds, by thereaction of the corresponding N-oxyl intermediate with a hydrocarbon inpresence of an organic hydroperoxide and an iodide catalyst.

4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and4-oxo-1-oxyl-2,2,6,6-tetramethylpiperidine are described as scavengersfor some carbon centered radicals (S. Nigam et al., J. Chem. Soc.,Trans. Faraday Soc., 1976, (72), 2324 and by K.-D. Asmus et al., Int. J.Radiat. Biol., 1976, (29), 211).

D. H. R. Barton et al., Tetrahedron, 1996, (52), 10301 describe theformation of some N-alkoxy-2,2,6,6-tetramethylpiperidine derivatives inthe reaction of hydrocarbons with iron(II) and iron(III) species,hydrogen peroxide and various coadditives in the presence ofN-oxyl-2,2,6,6-tetramethylpiperidine (TEMPO).

U.S. Pat. No. 5,374,729 describes a process for the preparation ofN-methoxy derivatives of hindered amines from the reaction of thecorresponding N-oxyl compound with methyl radicals produced fromdimethyl sulfoxide by decomposing aqueous hydrogen peroxide in presenceof a metal salt or by thermal decomposition of di-tert.butyl peroxide.

U.S. Pat. No. 4,921,962 describes a process for the formation ofN-hydrocarbyloxy derivatives of sterically hindered amines in which ahindered amine or N-oxyl substituted hindered amine is reacted with ahydrocarbon solvent in the presence of a hydroperoxide and a molybdenumcatalyst.

It has now been found that N-hydrocarbyloxy substituted stericallyhindered amines can most suitably be prepared from the N-oxylintermediate and a hydrocarbon in presence of an organic hydroperoxideand an iodide catalyst. The process of the invention uses only catalyticquantities of iodide and does not require high temperatures.

Thus, present invention pertains to a process for the preparation of anamine ether of a sterically hindered amine by reacting a correspondingsterically hindered aminoxide with an aliphatic hydrocarbon compound,characterized in that the reaction is carried out in the presence of anorganic hydroperoxide and an iodide, which is preferably used in acatalytic amount.

The aliphatic hydrocarbon compound may be any compound selected fromalkane, alkene, alkyne, or cyclic or polycyclic analogues thereof, andoptionally may be substituted, e.g. by aryl, halogen, alkoxy etc.,provided that an aliphatic CH (or CH₂, CH₃) moiety is contained.

Advantageously, the process of the invention is carried out in theabsence of a copper or a copper compound, preferably in the absence ofany heavy metal or heavy metal compound. Heavy metal is to be understoodas transition metal or any metal of higher molecular weight thancalcium. Metal compounds, the presence of which is advantageously to beavoided in the present process, include any form like salts, complexes,solutions and dispersions thereof. The amounts of these compounds to betolerated within the process of the invention are preferably well belowthe catalytic level, e.g. below 0.0001 molar equivalent per mole ofnitroxyl moiety, more preferably within or below the ppm-level (up to1000 parts by weight of heavy metal per 1 million parts by weight oftotal reaction mixture).

Preferred is a process for the preparation of an amine ether of theformula A

wherein

-   a is 1 or 2;-   when a is 1, E is E′-   when a is 2, E is L;

E′ is C₁-C₃₆ alkyl; C₃-C₁₈ alkenyl; C₂-C₁₈ alkinyl; C₅-C₁₈ cycloalkyl;C₅-C₁₈ cycloalkenyl; a radical of a saturated or unsaturated aliphaticbicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms; C₂-C₇alkyl orC₃-C₇alkenyl substituted by halogen, C₁-C₈alkoxy or phenoxy;C₄-C₁₂heterocycloalkyl; C₄-C₁₂heterocycloalkenyl; C₇-C₁₅ aralkyl orC₄-C₁₂heteroaralkyl, each of which is unsubstituted or substituted byC₁-C₄ alkyl or phenyl; or E′ is a radical of formula (VII) or (VIII)

-   Ar is C₆-C₁₀aryl or C₅-C₉heteroaryl;-   X is phenyl, naphthyl or biphenyl, which are substituted by 1, 2, 3    or 4 D and optionally further substituted by NO₂, halogen, amino,    hydroxy, cyano, carboxy, C₁-C₄alkoxy, C₁-C₄alkylthio,    C₁-C₄alkylamino or di(C₁-C₄alkyl)amino;-   D is a group    a group C(O)-G₁₃ or a group C(O)-G₉-C(O)-G₁₃;-   G₁ and G₂, independently of each other, are hydrogen, halogen, NO₂,    cyano, —CONR₅R₆, —(R₉)COOR₄, —C(O)—R₇, —OR₈, —SR₈, —NHR₈, —N(R₁₈)₂,    carbamoyl, di(C₁-C₁₈alkyl)carbamoyl, —C(═NR₅)(NHR₆), C₁-C₁₈alkyl;    C₃-C₁₈alkenyl; C₃-C₁₈alkinyl, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl or    C₂-C₁₂heterocycloalkyl; C₁-C₁₈alkyl or C₃-C₁₈alkenyl or    C₃-C₁₈alkinyl or C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl or    C₂-C₁₂heterocycloalkyl substituted by OH, halogen, NO₂, amino,    cyano, carboxy, COOR₂₁, C(O)—R₂₂, C₁-C₄alkoxy, C₁-C₄alkylthio,    C₁-C₄alkylamino or di(C₁-C₄alkyl)amino or a group —O—C(O)—R₇;    C₂-C₁₈alkyl which is interrupted by at least one O atom and/or NR₅    group; or are C₆-C₁₀aryl; or phenyl or naphthyl which are    substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen,    cyano, hydroxy, carboxy, COOR₂₁, C(O)—R₂₂, C₁-C₄alkylamino or    di(C₁-C₄alkyl)amino; or G₁ and G₂ together with the linking carbon    atom form a C₃-C₁₂cycloalkyl radical;-   G₅ and G₆ are independently of each other H or CH₃;-   G₉ is C₁-C₁₂alkylene or a direct bond;-   G₁₃ is C₁-C₁₈alkyl;-   G₁₄ is C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, an acyl radical of an    aliphatic or unsaturated aliphatic carboxylic or carbamic acid    containing 2 to 18 carbon atoms, an acyl radical of a cycloaliphatic    carboxylic or carbamic acid containing 7 to 12 carbon atoms, or acyl    radical of an aromatic acid containing 7 to 15 carbon atoms;-   G₅₅ is H, CH₃ or phenyl;-   G₆₆ is —CN or a group of the formula —COOR₄ or —CONR₅R₆ or    —CH₂—O-G₁₄;-   L is alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8    carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of    3 to 18 carbon atoms, alkylene of 1 to 12 carbon atoms substituted    by phenyl or by phenyl substituted by alkyl of 1 to 4 carbon atoms;    or is alkylene of 4 to 18 carbon atoms interrupted by COO and/or    phenylene;-   T′ is tertiary C₄-C₁₈alkyl or phenyl, each of which are    unsubstituted or substituted by halogen, OH, COOR₂₁ or C(O)—R₂₂; or    T′ is C₅-C₁₂cycloalkyl; C₅-C₁₂cycloalkyl which is interrupted by at    least one O or —NR₁₈—; a polycyclic alkyl radical having 7-18 carbon    atoms, or the same radical which is interrupted by at least one O or    —NR₁₈—; or T′ is —C(G₁)(G₂)-T″; or C₁-C₁₈alkyl or C₅-C₁₂cycloalkyl    substituted by-   T″ is hydrogen, halogen, NO₂, cyano, or is a monovalent organic    radical comprising 1-50 carbon atoms;-   or T″ and T′ together form a divalent organic linking group    completing, together with the hindered amine nitrogen atom and the    quaternary carbon atom substituted by G₁ and G₂, an optionally    substituted five- or six-membered ring structure;    and-   R₄ is hydrogen, C₁-C₁₈alkyl, phenyl, an alkali metal cation or a    tetraalkylammonium cation;-   R₅ and R₆ are hydrogen, C₁-C₁₈alkyl, C₂-C₁₈alkyl which is    substituted by hydroxy or, taken together, form a C₂-C₁₂alkylene    bridge or a C₂-C₁₂-alkylene bridge interrupted by O or/and NR₁₈;-   R₇ is hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl;-   R₈ is hydrogen, C₁-C₁₈alkyl or C₂-C₁₈hydroxyalkyl;-   R₉ is C₁-C₁₂alkylene or a direct bond;-   R₁₈ is C₁-C₁₈alkyl or phenyl, which are unsubstituted or substituted    by halogen, OH, COOR₂₁ or C(O)—R₂₂;-   R₂₁ is hydrogen, a alkali metal atom or C₁-C₁₈alkyl; and-   R₂₂ is C₁-C₁₈alkyl;    which process comprises

reacting a N-oxyl amine of formula B

with a compound of formula IV or VE′-H  (IV)H-L-H  (V)in the presence of an organic hydroperoxide and a catalytic amount of aniodide.

More specifically, present invention pertains to a process for thepreparation of an amine ether of the formula A

wherein

-   a is 1 or 2;-   when a is 1, E is E′-   when a is 2, E is L;-   E′ is C₁-C₃₆ alkyl; C₃-C₁₈ alkenyl; C₂-C₁₈ alkinyl; C₅-C₁₈    cycloalkyl; C₅-C₁₈ cycloalkenyl; a radical of a saturated or    unsaturated aliphatic bicyclic or tricyclic hydrocarbon of 7 to 12    carbon atoms; C₂-C₇alkyl or C₃-C₇alkenyl substituted by halogen;    C₇-C₁₅ aralkyl or C₇-C₁₅ aralkyl substituted by C₁-C₄ alkyl or    phenyl; or E′ is a radical of formula (VII)    wherein-   X is phenyl, naphthyl or biphenyl, which are substituted by 1, 2, 3    or 4 D and optionally further substituted by NO₂, halogen, amino,    hydroxy, cyano, carboxy, C₁-C₄alkoxy, C₁-C₄alkylthio,    C₁-C₄alkylamino or di(C₁-C₄alkyl)amino;-   D is a group    a group C(O)-G₁₃ or a group C(O)-G₉-C(O)-G₁₃;-   G₁ and G₂, independently of each other, are hydrogen, halogen, NO₂,    cyano, —CONR₅R₆, —(R₉)COOR₄, —C(O)—R₇, —OR₈, —SR₈, —NHR₈, —N(R₁₈)₂,    carbamoyl, di(C₁-C₁₈alkyl)carbamoyl, —C(═NR₅)(NHR₆), C₁-C₁₈alkyl;    C₃-C₁₈alkenyl; C₃-C₁₈alkinyl, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl or    C₂-C₁₂heterocycloalkyl; C₁-C₁₈alkyl or C₃-C₁₈alkenyl or    C₃-C₁₈alkinyl or C₇C₉phenylalkyl, C₃-C₁₂cycloalkyl or    C₂-C₁₂heterocycloalkyl substituted by OH, halogen, NO₂, amino,    cyano, carboxy, COOR₂₁, C(O)—R₂₂, C₁-C₄alkoxy, C₁-C₄alkylthio,    C₁-C₄alkylamino or di(C₁-C₄alkyl)amino or a group —O—C(O)—R₇;    C₂-C₁₈alkyl which is interrupted by at least one O atom and/or NR₅    group; or are C₆-C₁₀aryl; or phenyl or naphthyl which are    substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen,    cyano, hydroxy, carboxy, COOR₂₁, C(O)—R₂₂, C₁-C₄alkylamino or    di(C₁-C₄alkyl)amino; or G₁ and G₂ together with the linking carbon    atom form a C₃-C₁₂cycloalkyl radical;-   G₅ and G₆ are independently of each other H or CH₃;-   G₉ is C₁-C₁₂alkylene or a direct bond;-   G₁₃ is C₁-C₁₈alkyl;-   L is alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8    carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of    3 to 18 carbon atoms, alkylene of 1 to 12 carbon atoms substituted    by phenyl or by phenyl substituted by alkyl of 1 to 4 carbon atoms;-   T′ is tertiary C₄-C₁₈alkyl or phenyl, each of which are    unsubstituted or substituted by halogen, OH, COOR₂₁ or C(O)—R₂₂; or    T′ is C₅-C₁₂cycloalkyl; C₅-C₁₂cycloalkyl which is interrupted by at    least one O or —NR₁₈—; a polycyclic alkyl radical having 7-18 carbon    atoms, or the same radical which is interrupted by at least one O or    —NR₁₈—; or T′ is —C(G₁)(G₂)-T″; or C₁-C₁₈alkyl or C₅-C₁₂cycloalkyl    substituted by-   T′ is hydrogen, halogen, NO₂, cyano, or is a monovalent organic    radical comprising 1-50 carbon atoms;-   or T″ and T′ together form a divalent organic linking group    completing, together with the hindered amine nitrogen atom and the    quaternary carbon atom substituted by G₁ and G₂, an optionally    substituted five- or six-membered ring structure;    and-   R₄ is hydrogen, C₁-C₁₈alkyl, phenyl, an alkali metal cation or a    tetraalkylammonium cation;-   R₅ and R₆ are hydrogen, C₁-C₁₈alkyl, C₂-C₁₈alkyl which is    substituted by hydroxy or, taken together, form a C₂-C₁₂alkylene    bridge or a C₂-C₁₂-alkylene bridge interrupted by O or/and NR₁₈—;-   R₇ is hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl;-   R₈ is hydrogen, C₁-C₁₈alkyl or C₂-C₁₈hydroxyalkyl;-   R₉ is C₁-C₁₂alkylene or a direct bond;-   R₁₈ is C₁-C₁₈alkyl or phenyl, which are unsubstituted or substituted    by halogen, OH, COOR₂₁ or C(O)—R₂₂;-   R₂₁ is hydrogen, a alkali metal atom or C₁-C₁₈alkyl; and-   R₂₂ is C₁-C₁₈alkyl;    which process comprises

reacting a N-oxyl amine of formula B

with a hydrocarbon of formula IV or VE′-H  (IV)H-L-H  (V)in the presence of an organic hydroperoxide and a catalytic amount of aniodide.

In particular, present invention pertains to a process for the synthesisof a hindered amine of formula I or II

wherein

-   G₁, G₂, G₃ and G₄ independently of each other are C₁-C₁₈alkyl;    C₃-C₁₈alkenyl; C₃-C₁₈alkinyl; C₁-C₁₈alkyl or C₃-C₁₈alkenyl or    C₃-C₁₈alkinyl substituted by OH, halogen or a group —O—C(O)—R₅;    C₂-C₁₈alkyl which is interrupted by at least one O atom and/or NR₅    group; or are C₃-C₁₂cycloalkyl; or C₆-C₁₀aryl; or G₁ and G₂ and/or    G₃ and G₄ together with the linking carbon atom form a    C₃-C₁₂cycloalkyl radical;-   a is 1 or 2;-   when a is 1, E is E′, wherein E′ is C₁-C₃₆ alkyl; C₂-C₁₈ alkenyl;    C₂-C₁₈ alkinyl; C₅-C₁₈ cycloalkyl; C₅-C₁₈ cycloalkenyl; a radical of    a saturated or unsaturated aliphatic bicyclic or tricyclic    hydrocarbon of 7 to 12 carbon atoms; C₂-C₇alkyl or C₃-C₇alkenyl    substituted by halogen; C₇-C₁₅ aralkyl or C₇-C₁₅ aralkyl substituted    by C₁-C₄ alkyl or phenyl; or E′ is a radical of formula (VII)    wherein-   X is phenyl, naphthyl or biphenyl, which are substituted by 1, 2, 3    or 4 D and optionally further substituted by NO₂, halogen, amino,    hydroxy, cyano, carboxy, C₁-C₄alkoxy, C₁-C₄alkylthio,    C₁-C₄alkylamino or di(C₁-C₄alkyl)amino;-   D is a group    a group C(O)-G₁₃ or a group C(O)-G₉-C(O)-G₁₃;-   when a is 2, E is L;-   G₅ and G₆ are independently of each other H or CH₃;-   G₉ is C₁-C₁₂alkylene or a direct bond;-   G₁₃ is C₁-C₁₈alkyl;-   L is alkylene of 1 to 18 carbon atoms, cycloalkylene of 5 to 8    carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of    3 to 18 carbon atoms, alkylene of 1 to 12 carbon atoms substituted    by phenyl or by phenyl substituted by alkyl of 1 to 4 carbon atoms;-   T is a divalent organic radical required to complete formula I to    form, together with the hindered amine nitrogen atom and the two    quaternary carbon atoms substituted by G₁ and G₂ or G₃ and G₄, a    five- or six-membered ring structure;-   T₁ is hydrogen, halogen, NO₂, cyano, —(R₉)COOR₄, —(R₉)C(O)—R₇, —OR₈,    unsubstituted C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl,    C₇C₉phenylalkyl, C₃-C₁₂cycloalkyl or C₂-C₁₂heterocycloalkyl; or T₁    is C₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₂-C₁₈ alkynyl, C₇C₉phenylalkyl,    C₃-C₁₂cycloalkyl or C₂-C₁₂heterocycloalkyl, which is substituted by    NO₂, halogen, hydroxy, cyano, carboxy, C₁-C₆alkanoyl, C₁-C₁₂alkoxy;    or phenyl, naphthyl, which are unsubstituted or substituted by    C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen, cyano, hydroxy,    carboxy; or T₁ is a residue —CH₂—O—R₁₀ or —CH₂—NR₁₈—R₁₀ or    —C(═CH₂)—R₁₁ or —C(═O)—R₁₂;-   T₂ is tertiary C₄-C₁₈alkyl or phenyl, which are unsubstituted or    substituted by halogen, OH, COOR₂₁ or C(O)—R₂₂; or T₂ is    C₅-C₁₂cycloalkyl; C₅-C₁₂cycloalkyl which is interrupted by at least    one O; a polycyclic alkyl radical having 7-18 carbon atoms or the    same radical which is interrupted by at least one O atom; or T₂ is    —C(G₁)(G₂)-T₁; or-   R₄ is hydrogen, C₁-C₁₈alkyl, phenyl, an alkali metal cation or a    tetraalkylammonium cation;-   R₅ is hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl-   R₇ is hydrogen, C₁-C₁₈alkyl or phenyl;-   R₈ is hydrogen, C₁-C₁₈alkyl or C₂-C₁₈hydroxyalkyl;-   R₉ is C₁-C₁₂alkylene or a direct bond;-   R₁₀ is hydrogen, formyl, C₂-C₁₈alkylcarbonyl, benzoyl, C₁-C₁₈alkyl,    C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkyl interrupted by O or NR₁₈, or is    benzyl or phenyl which are unsubstituted or substituted by halogen,    OH, COOR₂₁ or C(O)—R₂₂;-   R₁₁ is OH, C₁-C₁₈alkoxy, benzyloxy, O—C(O)—(C₁-C₁)alkyl, N(R₁₈)₂, or    a group C(O)R₂₅;-   R₁₂ is OH, O(alkali-metal), C₁-C₁₈alkoxy, benzyloxy, N(R₁₈)₂;-   R₁₈ is C₁-C₁₈alkyl or C₂-C₁₈hydroxyalkyl;-   R₂₁ is hydrogen, a alkali metal atom or C₁-C₁₈alkyl; and-   R₂₂ is C₁-C₁₈alkyl;-   R₂₅ is OH, C₁-C₁₈alkoxy, benzyloxy, N(R₁₈)₂;    which process comprises    reacting a N-oxyl hindered amine of formula III or IIIa    with a hydrocarbon of formula IV or V    E′-H  (IV)    H-L-H  (V)    in the presence of an organic hydroperoxide and a catalytic amount    of an iodide.

In the context of the description of the present invention, the termalkyl comprises, for example, methyl, ethyl and the isomers of propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.Examples of aryl-substituted alkyl (aralkyl) are benzyl, α-methylbenzylor cumyl. Examples of alkoxy are methoxy, ethoxy, propoxy, butoxy,octyloxy etc. Examples of alkenyl are vinyl and especially allyl.Examples of alkylene including alkylidene are ethylene, n-propylene or1,2-propylene.

Some examples of cycloalkyl are cyclobutyl, cyclopentyl, cyclohexyl,methylcyclopentyl, dimethylcyclopentyl and methylcyclohexyl.

Examples of aryl are phenyl and naphthyl. Examples of substituted arylare methyl-, dimethyl-, trimethyl-, methoxy- or phenyl-substitutedphenyl.

Some examples of an aliphatic carboxylic acid are acetic, propionic,butyric, stearic acid. An example of a cycloaliphatic carboxylic acid iscyclohexanoic acid. An example of an aromatic carboxylic acid is benzoicacid. An example of a phosphorus-containing acid is methylphosphonicacid. An example of an aliphatic dicarboxylic acid is malonyl, maleoylor succinyl, or sebacic acid. An example of a residue of an aromaticdicarboxylic acid is phthaloyl.

A group heterocycloalkyl or heterocycloalkenyl embraces one or twoheteroatoms, and a group heteroaryl from one to four heteroatoms, theheteroatoms being preferably selected from the group consisting ofnitrogen, sulfur and oxygen. Some examples of heterocycloalkyl aretetrahydrofuryl, pyrrolidinyl, piperazinyl and tetrahydrothienyl. Someexamples of heteroaryl are furyl, thienyl, pyrrolyl, pyridyl andpyrimidinyl. C₂-C₁₂heterocycloalkyl is typically oxirane, 1,4-dioxane,tetrahydrofuran, γ-butyrolactone, ε-caprolactam, oxirane, aziridine,diaziridine, pyrrole, pyrrolidine, thiophen, furan, pyrazole, imidazole,oxazole, oxazolidine, thiazole, pyran, thiopyran, piperidine ormorpholine.

An example of a monovalent silyl radical is trimethylsilyl.

Polycyclic alkyl radicals which may also be interrupted by at least oneoxygen or nitrogen atom are for example adamantane, cubane, twistane,norbornane, bycyclo[2.2.2]octane bycyclo[3.2.1]octane,hexamethylentetramine (urotropine) or a group

Acyl radicals of monocarboxylic acids are, within the definitions, aresidue of the formula —CO—R″, wherein R″ may stand inter alia for analkyl, alkenyl, cycloalkyl or aryl radical as defined. Preferred acylradicals include acetyl, benzoyl, acryloyl, methacryloyl, propionyl,butyryl, valeroyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl,undecanoyl, dodecanoyl, pentadecanoyl, stearoyl. Polyacyl radicals ofpolyvalent acids are of the formula (—CO)_(n)—R″, wherein n is thevalency, e.g. 2, 3, 4, 5 or 6. Some preferred examples for such residuesare given elsewhere.

In preferred products of the instant process, E′ is selected from thegroup consisting of

(C₅-C₆cycloalkyl)₂CCN, (C₁-C₁₂alkyl)₂CCN, —CH₂CH═CH₂,(C₁-C₁₂)alkyl-CR₃₀—C(O)—(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₃₀—C(O)—(C₆-C₁₀)aryl,(C₁-C₁₂)alkyl-CR₃₀—C(O)—(C₁-C₁₂)alkoxy, (C₁-C₁₂)alkyl-CR₃₀—C(O)-phenoxy,(C₁-C₁₂)alkyl-CR₃₀—C(O)—N-di(C₁-C₁₂)alkyl,(C₁-C₁₂)alkyl-CR₃₀—CO—NH(C₁-C₁₂)alkyl, (C₁-C₁₂)alkyl-CR₃₀—CO—NH₂,—CH₂CH═CH—CH₃, —CH₂—C(CH₃)═CH₂, —CH₂—CH═CH-phenyl,

(C₁-C₁₂)alkyl-CR₃₀—CN,

wherein

-   R₃₀ is hydrogen or C₁-C₁₂alkyl;-   the aryl groups are phenyl or naphthyl, which are unsubstituted or    substituted with C₁-C₁₂alkyl, halogen, C₁-C₁₂alkoxy, formyl,    C₂-C₁₂alkylcarbonyl, glycidyloxy, OH, —COOH or —COOC₁-C₁₂alkyl. More    preferably E′ is selected from the group consisting of —CH₂-phenyl,    CH₃CH-phenyl, (CH₃)₂C-phenyl, (C₅-C₆cycloalkyl)₂CCN, (CH₃)₂CCN,    —CH₂CH═CH₂, CH₃CH—CH═CH₂(C₁-C₈alkyl) CR₃₀—C(O)-phenyl,    (C₁-C₈)alkyl-CR₃₀—C(O)—(C₁-C₈)alkoxy,    (C₁-C₈)alkyl-CR₃₀—C(O)—(C₁-C₈)alkyl,    (C₁-C₈)alkyl-CR₃₀—C(O)—N-di(C₁-C₈)alkyl,    (C₁-C₈)alkyl-CR₃₀—C(O)—NH(C₁-C₈)alkyl, (C₁-C₈)alkyl-CR₃₀—C(O)—NH₂,    (C₁-C₁₂)alkyl-CR₃₀—CN, wherein R₃₀ is hydrogen or (C₁-C₈)alkyl.

G₁ and G₂ and/or G₃ and G₄ forming, together with the linking carbonatom, a C₃-C₁₂cycloalkyl radical, preferably form a C₅-C₁₂cycloalkylradical, especially cyclopentylene, cyclohexylene or cycloheptylene.

G₁, G₂, G₃ and G₄ independently are preferably alkyl of 1 to 4 carbonatoms, or the adjacent radicals G₁ and G₂ and/or G₃ and G₄ together arepentamethylene. More preferably, G₁, G₂, G₃ and G₄ independently aremethyl or ethyl or propyl, especially methyl or ethyl. In the productsmost preferred, G₁ and G₃ are each methyl while G₂ and G₄ independentlyare methyl, ethyl or propyl.

T usually is an organic linking group containing 2-500 carbon atoms andforming, together with the carbon atoms it is directly connected to andthe nitrogen atom, a substituted, 5-, 6 or 7-membered cyclic ringstructure; T is preferably a C₂-C₅₀₀hydrocarbon optionally containing1-200 hetero atoms selected from nitrogen, oxygen, phosphorus, sulfur,silicon and halogen, T therein can be part of a 6-membered cyclic ringstructure. More preferably, T is an organic linking group of the formula

wherein

-   E₂ is —CO— or —(CH₂)_(b)—, while b is 0, 1 or 2;-   E₁ is a carbon atom carrying the two residues R₂₄ and R₂₅, or is    >N—R₂₅, or is oxygen, and R₂₄ and R₂₅ are hydrogen or an organic    residue, characterized in that the linking group T in total contains    2-500 carbon atoms and forms, together with the carbon atoms it is    directly connected to it and the nitrogen atom, a substituted, 5-, 6    or 7-membered cyclic ring structure, or wherein R₂₄ and R₂₅ together    are ═O or wherein R₂₄ is hydrogen and R₂₅ is hydrogen or hydroxy. T    is most preferably 2-hydroxy-1,3-propanediyl or    2-oxo-1,3-propanediyl.-   Preferred products of the formula (I) are those wherein G₁, G₂, G₃    and G₄, independently of each other, are methyl, ethyl, phenyl or    COOR₄;-   E is a carbon centered radical formed from a C₇-C₁₁phenylalkane or a    C₆-C₁₀pyridylalkane; or C₅-C₁₂cycloalkane; or C₅-C₁₂cycloalkene; or    an oxacyclohexane or oxycyclohexene; or C₃-C₈alkene; or C₃-C₈alkene    substituted by phenoxy; or a benzene which is substituted by    C₁-C₄alkyl and a further substituent selected from C₁-C₄alkoxy,    glycidyl or glycidyloxy; or E is a radical of formula (VIII)    wherein-   Ar is C₆-C₁₀aryl or C₅-C₉heteroaryl;-   G₁₄ is C₁-C₄alkyl or an acyl radical of an aliphatic carboxylic acid    containing 2 to 4 carbon atoms or benzoyl;-   G₅₅ is H, CH₃ or phenyl;-   G₆₆ is —CN or a group of the formula —COOR₄ or —CH₂—O-G₁₄;-   R₄ is hydrogen or C₁-C₈alkyl;-   L is a carbon centered radical formed from propane, butane, pentane,    2,2-dimethyl-propane, xylene; and-   T is phenylene or an organic linking group of the formula    wherein-   E₂ is —CO— or —(CH₂)_(b)—, while b is 0, 1 or 2;-   E₁ is a carbon atom carrying the two residues R₂₄ and R₂₅, or is    >N—R₂₅, or is oxygen, and R₂₄ and R₂₅ are hydrogen or an organic    residue, characterized in that the linking group T in total contains    2-500 carbon atoms and forms, together with the carbon atoms it is    directly connected to it and the nitrogen atom, a substituted, 5-, 6    or 7-membered cyclic ring structure, or wherein R₂₄ and R₂₅ together    are ═O or wherein R₂₄ is hydrogen and R₂₅ is hydrogen or hydroxy;-   or E₁ and E₂ together are 1,2-phenylene.

The product of formula A most preferably corresponds to one of theformulae

wherein

-   G₁, G₂, G₃ and G₄ independently of each other are C₁-C₁₈alkyl;    C₃-C₁₈alkenyl; C₃-C₁₈alkinyl; C₁-C₁₈alkyl or C₃-C₁₈alkenyl or    C₃-C₁₈alkinyl substituted by OH, halogen or a group —O—C(O)—R₅;    C₂-C₁₈alkyl which is interrupted by O; C₅-C₁₂cycloalkyl; or phenyl;    or G₁ and G₂ and/or G₃ and G₄ together with the linking carbon atom    form a C₅-C₁₂cycloalkyl radical;-   Z, is O or NR₈;-   R₈ is hydrogen, OH, C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl,    C₁-C₁₈alkyl, C₃-C₁₈alkenyl, C₃-C₁₈alkinyl which are substituted by    one or more OH, halogen or a group —O—C(O)—N, C₂-C₁₈alkyl which is    interrupted by at least one O atom and/or NR₅ group,    C₃-C₁₂cycloalkyl or C₆-C₁₀aryl, C₇-C₉phenylalkyl, C₅-C₁₀heteroaryl,    —C(O)—C₁-C₁₈alkyl, —O—C₁-C₁₈alkyl or —COOC₁-C₁₈alkyl;-   Q is a direct bond or a divalent radical CR₉R₁₀, CR₉R₁₀—CR₁₁R₁₂,    CR₉R₁₀CR₁₁R₁₂CR₁₃R₁₄, C(O) or CR₉R₁₀C(O);-   R₉, R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄ are independently hydrogen, phenyl,    or C₁-C₁₈alkyl;-   T is CH₂—C(R₂₄)(R₂₅)—CH₂, wherein R₂₄ and R₂₅ together are ═O or    independently are H, OH or an organic residue, characterized in that    the linking group T in total contains 2-500 carbon atoms and    optionally 1-200 hetero atoms selected from, oxygen, phosphorus,    sulfur, silicon, halogen and tertiary nitrogen.

The sterically hindered aminoxides, also referred to as N-oxyl eductsfor the instant process which include compounds of formulae B, III orIIIa, are largely known in the art; they may be prepared by oxidation ofthe corresponding N—H hindered amine with a suitable oxygen donor, e.g.by the reaction of the corresponding N—H hindered amine with hydrogenperoxide and sodium tungstate as described by E. G. Rozantsev et al., inSynthesis, 1971, 192; or with tert-butyl hydroperoxide and molybdenum(VI) as taught in U.S. Pat. No. 4,691,015, or obtained in analogousmanner.

The preferred amount of hydrocarbon for the instant process depends tosome extent on the relative number of reactive hydrogens on thehydrocarbon reactant and the hindered amine nitroxyl compound. Thereaction is typically carried out with a ratio of 1 to 100 moles ofhydrocarbon per mole of nitroxyl moiety with the preferred ratio being 1to 50 moles per mole of nitroxyl moiety, and the most preferred ratiobeing 1 to 30 moles of hydrocarbon per mole of nitroxyl moiety.

The preferred amount of organic hydroperoxide is 1 to 20 moles per moleof nitroxyl moiety, with the more preferred amount being 1 to 5 moles ofperoxide per mole of nitroxyl moiety and the most preferred amount being1 to 3 moles of peroxide per mole of nitroxyl moiety.

The organic hydroperoxide used in the process of present invention canbe of the formula R—OOH, wherein R usually is a hydrocarbon containing1-18 carbon atoms. The organic hydroperoxide preferably is aperoxoalcohol containing 3-18 carbon atoms. R is often aliphatic,preferably C₁-C₁₂alkyl. Most preferred organic hydroperoxide istert.butyl hydroperoxide.

The preferred amount of iodide catalyst is from about 0.0001 to 0.5,especially 0.0005 to 0.1 molar equivalent per mole of nitroxyl moiety,with a ratio of 0.001 to 0.05 moles of iodide per mole of nitroxylmoiety being the most preferred.

The reaction is preferably run at 0° to 100° C.; more preferably at 20°to 100° C., especially in the range 20-80° C.

More specifically, the instant process involves the reaction of amixture of 1 to 100 moles of the hydrocarbon, e.g. of formula IV or V, 1to 20 moles of organic hydroperoxide, and 0.001 mmoles to 0.5 moles ofiodide catalyst per mole of N-oxyl compound, such as the compound offormula B (1 mmol is 0.001 mol). Preferably, the molar ratio of iodidecatalyst per mole of N-oxyl compound is in the range from 1:100 to1:100000, especially 1:300 to 1:100000.

E is preferably a carbon centered radical formed from aC₇-C₁₁phenylalkane or a C₆-C₁₀pyridylalkane; or C₅-C₁₂cycloalkane; orC₅-C₁₂cycloalkene; or an oxacyclohexane or oxycyclohexene; orC₃-C₈alkene; or C₃-C₈alkene substituted by phenoxy; or a benzene whichis substituted by C₁-C₄alkyl and a further substituent selected fromC₁-C₄alkoxy, glycidyl or glycidyloxy; or E is a radical of formula(VIII)

wherein

-   Ar is C₆-C₁₀aryl or C₅-C₉heteroaryl;-   G₁₄ is C₁-C₄alkyl or an acyl radical of an aliphatic carboxylic acid    containing 2 to 4 carbon atoms or benzoyl;-   G₅₅ is H, CH₃ or phenyl;-   G₆₆ is —CN or a group of the formula —COOR₄ or —CH₂—O-G₁₄;-   R₄ is hydrogen or C₁-C₈alkyl;-   L is a carbon centered radical formed from propane, butane, pentane,    2,2-dimethyl-propane, xylene.

Important are those educts, which are pure hydrocarbons.

The educt hydrocarbon, such as compound of formula IV or V, may servetwo functions both as reactant and as solvent for the reaction. Thereaction can also be carried out using an inert organic or inorganicsolvent. A mixture of products may result if the hydrocarbon containsnon-equivalent carbon-hydrogen bonds which are reactive in the instantprocess. For example, cyclohexane can give only one product whereasisopentane can give three distinct reaction products.

Usually the hydrocarbon reactand, e.g. compound of formula IV or V,reacts with its most active aliphatic carbon-hydrogen bond.

A solvent may be used, especially if the hydrocarbon, such as thecompound of of formula IV or V, is a solid at the temperature of thereaction or if the catalyst is not very soluble in the hydrocarbon.Inert solvents should have less active carbon-hydrogen bonds; typicalinert solvents are acetonitrile, aromatic hydrocarbons like benzene,chlorobenzene, CCl₄, alcohols (e.g. methanol, ethanol, ethylene glycol,ethylene glycol monomethyl ether), or, especially for reactions withactivated hydrocarbons like alkylated aromats or alkenes, also alkaneslike hexane, decane etc., or mixtures thereof. Inorganic solvents suchas water are possible as well. The reaction can be carried out in oneliquid phase or in separate phases.

Good results can be achieved when phase transfer catalysts such asquaternary ammonium or phosphonium salts are used. For example,quaternary ammonium or phosphonium halogenides such as chlorides orbromides may be employed for this purpose. The structure of the ammoniumor phosphonium cation is less important; usually, quaternary ammonium orphosphonium cations contain 4 hydrocarbon residues bonded to the centralnitrogen or phosphorus atom, which may be, for example, alkyl,phenylalkyl or phenyl groups. Some readily available materials aretetra-C₁-C₁₂alkylated.

The iodide catalyst may be selected from any iodide compound, includingorganic and inorganic iodide compounds. Examples are alkaline oralkaline earth metal iodides, or onium iodides such as ammonium orphosphonium or sulfonium iodides. Suitable metal iodides are, interalia, those of lithium, sodium, potassium, magnesium or calcium.

Especially good results can be achieved when onium iodides are usedwhich are soluble in organic solvents. Suitable onium iodides embracequaternary ammonium, phosphonium or sulfonium iodides. The structure ofthe onium cation is less important provided the solubility in organicsolvents is high enough; the latter can be increased by increasing thehydrophobicity of the hydrocarbon residues attached to the onium cation.Some readily available materials are tetra-C₁-C₁₂alkylated ammoniumiodides and/or the following compounds:

-   Tetrabutylammonium iodide;-   Tetraoctylammonium iodide;-   Tetra(hexadecyl)ammonium iodide;-   Tetradodecylammonium iodide;-   Tetrahexylammonium iodide;-   Di-octadecyl-dimethyl-ammonium iodide;-   Hexadecyl-benzyl-dimethyl-ammonium iodide;-   Tributyl-methyl-ammonium iodide^(A));-   Di-tetradecyl-dimethyl-ammonium iodide;-   Trioctyl-propyl-ammonium iodide;-   Octyl-benzyl-dimethyl ammonium iodide;-   Trioctylmethylammonium iodide^(B));-   Hexadecylpyridinium iodide;-   Dioctyl-dimethyl-ammonium iodide;-   Octyl-trimethylammonium iodide;-   Tetraethyl ammonium iodide;-   Dioctyl-methyl sulfonium iodide;-   Tetraphenylphosphonium iodide;-   Triphenyl-isopropyl phosphonium iodide;-   Triphenylethylphosphonium iodide;-   Triphenylhexylphosphonium iodide;-   Tetrabutyl phosphonium iodide;-   Tributyl-hexadecyl phosphonium iodide;-   Tetraoctyl phosphonium iodide;-   Triphenylmethyl phosphonium iodide;-   Diphenyl-dimethyl-phosphonium iodide;-   Tetraethylphosphonium iodide;-   Phenyl-trimethyl-phosphonium iodide;-   Triphenyl-(CH₂CO₂CH₃)phosphonium iodide;-   Triphenylbenzylphosphonium iodide.-   A) iodide form of ALIQUAT® 175-   B) iodide form of ALIQUAT® 336

In a preferred embodiment, the iodide catalyst functions the same timeas a phase transfer catalyst, e.g. when a quaternary ammonium orphosphonium iodide such as tetrabutylammoniumiodide is used as catalyst.These compounds are known, many are commercially available.

The onium iodides can be generated from any other onium salt (e.g.,hydroxide, sulfate, hydrogensulfate, fluoride, acetate, chloride,cyanide, bromide, nitrate, nitrite, perchlorate etc.) via insitu anionexchange using a watersoluble inorganic iodide such as alkaline oralkaline earth metal iodides, other iodine containing salts or elementaliodine. For example, commercial onium chlorides of the ALIQUAT® seriesmay conveniently be brought into the above iodide form by in situ anionexchange.

The onium iodides can be bound to an organic or inorganic polymerbackbone, rendering a homogeneous or heterogenous catalytic system.

Preferably, the pH of the aqueous phase, if present, is held between 7and 11, especially between 9 and 10, most preferably at 9 during thereaction.

Preferred are quaternary ammonium or phosphonium iodides, especiallytetraalkyl ammonium iodides.

The instant process can be run in air or in an inert atmosphere such anitrogen or argon. The instant process can be run under atmosphericpressure as well as under reduced or elevated pressure. Elevatedpressure can especially be useful in reactions with a hydrocarbon, whichis gaseous under atmospheric pressure and the reaction temperature; inthis case, pressure/temperature conditions are advantageous where thehydrocarbon forms a liquid phase or is at least partially dissolved in asuitable solvent.

There are several variations of the instant process. One variationinvolves the addition of a solution of organic hydroperoxide to amixture of the N-oxyl hindered amine, the hydrocarbon and cosolvent (ifused), and catalyst which has been brought to the desired temperaturefor reaction. The proper temperature may be maintained by controllingthe rate of peroxide addition and/or by using a heating or cooling bath.After the hydroperoxide is added, the reaction mixture is convenientlystirred till the starting N-oxyl, e.g. compound of formula III, hasdisappeared or is no longer being converted to the desired product, e.g.compound of formula I and/or II. The reaction can be monitored bymethods known in the art such as UV-Vis spectroscopy, thin layerchromatography, gas chromatography or liquid chromatography. Additionalportions of catalyst can be added while the reaction is in progress.After the initial hydroperoxide charge has been added to the reactionmixture, more hydroperoxide can be added dropwise to bring the reactionto completion.

A second variation of the instant process is to simultaneously addseparate solutions of the hydroperoxide and the nitroxyl compound to amixture of the hydrocarbon, cosolvent (if used) and catalyst. Thenitroxyl compound may be dissolved in water or the alcohol solvent usedin the reaction. Some of the nitroxyl compound may be introduced intothe reaction mixture prior to starting the peroxide addition, and all ofthe nitroxyl compound should be added prior to completing the peroxideaddition.

Another variation of the instant process involves the simultaneousaddition of separate solutions of the hydroperoxide and of the aqueousor alcohol solution of the catalyst to a mixture of the nitroxylcompound, hydrocarbon, and cosolvent (if used). Some of the metal may beintroduced into the reaction mixture prior to starting the peroxideaddition.

Still another variation of the instant process is the simultaneousaddition of separate solutions of the hydroperoxide, of the aqueous oralcohol solution of the nitroxyl compound, and of an aqueous or alcoholsolution of the catalyst to the hydrocarbon and cosolvent (if used). Aportion of the nitroxyl compound and/or catalyst may be introduced intothe reaction mixture prior to starting the hydroperoxide addition. Allof the nitroxyl compound should be added prior to completing thehydroperoxide addition.

At the end of the reaction, the residual hydroperoxide should becarefully decomposed prior to the isolation of any products.

Examples for compounds which can be obtained advantageously with theprocess of present invention are those of formulae 1-28:

wherein in formulas (1) to (15):

-   -   m is 0 or 1;    -   R₁ is hydrogen, hydroxyl or hydroxymethyl;    -   R₂ is hydrogen, alkyl of 1 to 12 carbon atoms or alkenyl of 2 to        12 carbon atoms;    -   n is 1 to 4;    -   when n is 1,    -   R₃ is alkyl of 1 to 18 carbon atoms,        alkoxycarbonylalkylenecarbonyl of 4 to 18 carbon atoms, alkenyl        of 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl,        2-hydroxy or 2-(hydroxymethyl) substituted alkyl of 3 to 12        carbon atoms which alkyl is interrupted by oxygen, an acyl        radical of an aliphatic or unsaturated aliphatic carboxylic or        carbamic acid containing 2 to 18 carbon atoms, an acyl radical        of a cycloaliphatic carboxylic or carbamic acid containing 7 to        12 carbon atoms, or acyl radical of an aromatic acid containing        7 to 15 carbon atoms;    -   when n is 2,    -   R₃ is alkylene of 2 to 18 carbon atoms, a divalent acyl radical        of an aliphatic or unsaturated aliphatic dicarboxylic or        dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl        radical of a cycloaliphatic dicarboxylic or dicarbamic acid        containing 7 to 12 carbon atoms, or a divalent acyl radical of        an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;    -   when n is 3,    -   R₃ is a trivalent acyl radical of an aliphatic or unsaturated        aliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or        a trivalent acyl radical of an aromatic tricarboxylic acid        containing 9 to 15 carbon atoms;    -   when n is 4,    -   R₃ is a tetravalent acyl radical of an aliphatic or unsaturated        aliphatic tetracarboxylic acid, especially        1,2,3,4-butanetetracarboxylic acid,        1,2,3,4-but-2-enetetracarboxylic acid,        1,2,3,5-pentanetetracarboxylic acid and        1,2,4,5-pentanetetracarboxylic acid, or R₃ is a tetravalent acyl        radical of an aromatic tetracarboxylic acid containing 10 to 18        carbon atoms;    -   p is 1 to 3,    -   R₄ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6        carbon atoms;    -   when p is 1,    -   R₅ is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical        of an aliphatic or unsaturated aliphatic carboxylic or carbamic        acid containing 2 to 18 carbon atoms; an acyl radical of a        cycloaliphatic carboxylic or carbamic acid containing 7 to 12        carbon atoms, an acyl radical of an aromatic carboxylic acid        containing 7 to 15 carbon atoms, or R₄ and R₅ together are        —(CH₂)₅CO—, phthaloyl or a divalent acyl radical of maleic acid;    -   when p is 2,    -   R₅ is alkylene of 2 to 12 carbon atoms, a divalent acyl radical        of an aliphatic or unsaturated aliphatic dicarboxylic or        dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl        radical of a cycloaliphatic dicarboxylic or dicarbamic acid        containing 7 to 12 carbon atoms, or a divalent acyl radical of        an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;    -   when p is 3,    -   R₅ is a trivalent acyl radical of an aliphatic or unsaturated        aliphatic tricarboxylic acid containing 6 to 18 carbon atoms, or        a trivalent acyl radical of an aromatic tricarboxylic acid        containing 9 to 15 carbon atoms;    -   when n is 1,    -   R₆ is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18        carbon atoms, —NHalkyl of 1 to 18 carbon atoms or —N(alkyl)₂ of        2 to 36 carbon atoms,    -   when n is 2,    -   R₆ is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of        2 to 18 carbon atoms, —NH-alkylene-NH— of 2 to 18 carbon atoms        or —N(alkyl)-alkylene-N(alkyl)- of 2 to 18 carbon atoms, or R₆        is 4-methyl-1,3-phenylenediamino,    -   when n is 3,    -   R₆ is a trivalent alkoxy radical of a saturated or unsaturated        aliphatic triol containing 3 to 18 carbon atoms,    -   when n is 4,    -   R₆ is a tetravalent alkoxy radical of a saturated or unsaturated        aliphatic tetraol containing 4 to 18 carbon atoms,    -   R₇ and R₈ are independently chlorine, alkoxy of 1 to 18 carbon        atoms, —O-T₁, amino substituted by 2-hydroxyethyl, —NH(alkyl) of        1 to 18 carbon atoms, —N(alkyl)T₁ with alkyl of 1 to 18 carbon        atoms, or —N(alkyl)₂ of 2 to 36 carbon atoms,    -   R₉ is oxygen, or R₉ is nitrogen substituted by either hydrogen,        alkyl of 1 to 12 carbon atoms or T₁        T₁ is    -   R₁₀ is hydrogen or methyl,    -   q is 2 to 8,    -   R₁₁ and R₁₂ are independently hydrogen or the group T₂    -   R₁₃ is hydrogen, phenyl, straight or branched alkyl of 1 to 12        carbon atoms, alkoxy of 1 to 12 carbon atoms, straight or        branched alkyl of 1 to 4 carbon atoms substituted by phenyl,        cycloalkyl of 5 to 8 carbon atoms, cycloalkenyl of 5 to 8 carbon        atoms, alkenyl of 2 to 12 carbon atoms, glycidyl, allyloxy,        straight or branched hydroxyalkyl of 1 to 4 carbon atoms, or        silyl or silyloxy substituted three times independently by        hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by        alkoxy of 1 to 4 carbon atoms;    -   R₁₄ is hydrogen or silyl substituted three times independently        by hydrogen, by phenyl, by alkyl of 1 to 4 carbon atoms or by        alkoxy of 1 to 4 carbon atoms;    -   d is 0 or 1;    -   h is 0 to 4;    -   k is 0 to 5;    -   x is 3 to 6;    -   y is 1 to 10;    -   z is an integer such that the compound has a molecular weight of        1000 to 4000 amu, e.g. z may be from the range 3-10;    -   R₁₅ is morpholino, piperidino, 1-piperizinyl, alkylamino of 1 to        8 carbon atoms, especially branched alkylamino of 3 to 8 carbon        atoms such as tert-octylamino, —N(alkyl)T₁ with alkyl of 1 to 8        carbon atoms, or —N(alkyl)₂ of 2 to 16 carbon atoms,    -   R₁₆ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl        substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl        substituted once by chlorine and once by R₁₅, or s-triazinyl        substituted twice by R₁₅ with the condition that the two R₁₅        substituents may be different;    -   R₁₇ is chlorine, amino substituted by alkyl of 1 to 8 carbon        atoms or by T₁, —N(alkyl)T₁ with alkyl of 1 to 8 carbon atoms,        —N(alkyl)₂ of 2 to 16 carbon atoms, or the group T₃    -   R₁₈ is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl        substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl        substituted twice by —N(alkyl)₂ of 2 to 16 carbon atoms or        s-triazinyl substituted twice by —N(alkyl)T₁ with alkyl of 1 to        8 carbon atoms;    -   in formulas (16) to (28), R₁, R₂, R₇, R₈, R₉, R₁₀, R₁₃, R₁₄, d,        h, k, m, q, and T₁ have the same meanings as in formulas (1) to        (15);    -   R₁₉ is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl of 2 to        18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or        2-(hydroxymethyl) substituted alkyl of 3 to 12 carbon atoms        which alkyl is interrupted by oxygen, an acyl radical of an        aliphatic or unsaturated aliphatic carboxylic or carbamic acid        containing 2 to 18 carbon atoms, an acyl radical of a        cycloaliphatic carboxylic or carbamic acid containing 7 to 12        carbon atoms, or acyl radical of an aromatic acid containing 7        to 15 carbon atoms;    -   R₂₀ is alkylene of 2 to 18 carbon atoms, a divalent acyl radical        of an aliphatic or unsaturated aliphatic dicarboxylic or        dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl        radical of a cycloaliphatic dicarboxylic or dicarbamic acid        containing 7 to 12 carbon atoms, or a divalent acyl radical of        an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;    -   R₂₁ is hydrogen, alkyl of 1 to 18 carbon atoms or acyl of 2 to 6        carbon atoms;    -   R₂₂ is hydrogen, alkyl of 1 to 18 carbon atoms, an acyl radical        of an aliphatic or unsaturated aliphatic carboxylic or carbamic        acid containing 2 to 18 carbon atoms, an acyl radical of a        cycloaliphatic carboxylic or carbamic acid containing 7 to 12        carbon atoms, an acyl radical of an aromatic carboxylic acid        containing 7 to 15 carbon atoms, or R₄ and R₅ together are        —(CH₂)₅CO—, phthaloyl or a divalent acyl radical of maleic acid;    -   R₂₃ is hydrogen, alkyl of 1 to 4 carbon atoms or acyl of 2 to 6        carbon atoms;    -   R₂₄ is alkylene of 2 to 18 carbon atoms, a divalent acyl radical        of an aliphatic or unsaturated aliphatic dicarboxylic or        dicarbamic acid containing 2 to 18 carbon atoms, a divalent acyl        radical of a cycloaliphatic dicarboxylic or dicarbamic acid        containing 7 to 12 carbon atoms, or a divalent acyl radical of        an aromatic dicarboxylic acid containing 8 to 15 carbon atoms;    -   R₂₅ is alkoxy of 1 to 18 carbon atoms, alkenyloxy of 2 to 18        carbon atoms, —NHalkyl of 1 to 18 carbon atoms or —N(alkyl)₂ of        2 to 36 carbon atoms,    -   R₂₆ is alkylenedioxy of 2 to 18 carbon atoms, alkenylenedioxy of        2 to 18 carbon atoms, —NH-alkylene-NH— of 2 to 18 carbon atoms        or —N(alkyl)-alkylene-N(alkyl)- of 3 to 18 carbon atoms.        -   E is a carbon centered radical formed preferably from a            C₇-C₁₁phenylalkane, especially toluene, ethylbenzene,            isopropylbenzene; or C₅-C₁₂cycloalkane, especially            cyclohexene; or C₅-C₁₂cycloalkene, especially cyclohexene;            or C₃-C₈alkene, especially propene; or a benzene which is            substituted by C₁-C₄alkyl and a further substituent selected            from C₁-C₄alkoxy, glycidyl or glycidyloxy.        -   L is a carbon centered radical formed preferably from            propane, butane, pentane, 2,2-dimethyl-propane, xylene,            diethylbenzene.

Preferably, the reaction site in the compound E-H or H-L-H is anactivated carbon-hydrogen bond, whose carbon, for example, is linked toan electron pushing functional group or a functional group able tostabilize the radical formed after cleavage of the carbon-hydrogen bond.Electron withdrawing groups, if present in E-H or H-L-H, are preferablynot directly linked to the reactive site.

Products of the present process can be employed with advantage forstabilizing organic material against the damaging effect of light,oxygen and/or heat, especially for stabilizing synthetic organicpolymers or compositions containing them. They are notable for highthermal stability, substrate compatibility and good persistence in thesubstrate.

The compounds made by the instant process are particularly effective inthe stabilization of polymer compositions against harmful effects oflight, oxygen and/or heat; they are also useful as initiators orregulators for radical polymerization processes which providehomopolymers, random copolymers, block copolymers, multiblockcopolymers, graft copolymers and the like, at enhanced rates ofpolymerization and enhanced monomer to polymer conversions.

Of particular interest is the use of products of the present process asstabilizers in synthetic organic polymers, for example a coating or abulk polymer or article formed therefrom, especially in thermoplasticpolymers and corresponding compositions as well as in coatingcompositions. Thermoplastic polymers of most importance in presentcompositions are polyolefines and their copolymers, thermoplasticpolyolefin (TPO), thermoplastic polyurethan (TPU), thermoplastic rubber(TPR), polycarbonate, such as in item 19 above, and blends, such as initem 28 above. Of utmost importance are polyethylene (PE), polypropylene(PP), polycarbonate (PC) and polycarbonate blends such as PC/ABS blends,as well as in acid or metal catalyzed coating compositions.

In general the products of present invention may be added to thematerial to be stabilized in amounts of from 0.1 to 10%, preferably from0.01 to 5%, in particular from 0.01 to 2% (based on the material to bestabilized). Particular preference is given to the use of the novelcompounds in amounts of from 0.05 to 1.5%, especially from 0.1 to 0.5%.Where compounds of present invention are used as flame retardants,dosages are usually higher, e.g. 0.1 to 25% by weight, mainly 0.1 to 10%by weight of the organic material to be stabilized and protected againstinflammation.

Used in polymerizable compositions as a polymerization regulator orinitiator, preferably the regulator/initiator compound is present in anamount of from 0.01 mol-% to 30 mol-%, more preferably in an amount offrom 0.1 mol-% to 20 mol-% and most preferred in an amount of from 0.5mol-% to 10 mol-% based on the monomer or monomer mixture.

The following examples are for illustrative purposes only and are not tobe construed to limit the instant invention in any manner whatsoever.Percentages given are usually percent by weight if not otherwiseindicated. Abbreviations used:

-   min. minutes;-   HPLC high pressure liquid chromatography;-   GC gas chromatography;-   Bu butyl;-   Ph phenyl;-   Me methyl;-   Oct octyl;-   Hex hexyl;-   Et ethyl;-   Bz benzyl;-   Py 1-pyridinium;-   TEMPO 2,2,6,6-tetramethylpiperidine-N-oxide;-   eq. equivalent (of nitroxide, if not otherwise indicated).

EXAMPLE 1 Preparation of the Compound of Formula

To a stirred mixture of 5 g (32 mmol)2,2,6,6-tetramethylpiperidine-N-oxide (TEMPO), 34 g (320 mmol) ofethylbenzene and 0.12 g (0.32 mmol) of tetrabutylammoniumiodide, 6.2 g(48 mmol) of t-butylhydroperoxid (70% aqueous solution) are added at 60°C. within 30 minutes. The temperature is maintained at 60° C. for 25minutes until all of the TEMPO has reacted. The reaction mixture iscooled down to 25° C. and stirred with 61 g of an aqueous solution ofNa₂SO₃ (10%) until the disappearance of excess t-butylhydroperoxide. Theaqueous phase is then separated and washed with ethylbenzene. Thecombined organic phases are washed with brine, dried over MgSO₄,filtered, and the solvent is distilled off on a rotary-evaporator. Thecrude product is purified by flash-chromatography (silica gel,hexane:ethylacetate 9:1), yielding 5 g (60% of theory) of a yellow oil.Analysis required for C₁₇H₂₇NO (261.41): C, 78.11%, H, 10.41%, N, 5.36%;found: C, 78.04%, H, 10.46%, N, 5.26%. ¹H-NMR (CDCl₃), δ (ppm): 0.66(broad s, 3H), 1.03-1.52 (m, 15H), 1.48 (d, J=8 Hz, 3H), 4.78 (q, J=8Hz, 1H), 7.21-7.33 (m, 5H).

EXAMPLE 2

Example 1 is repeated except that 32 mmol of2,2,6,6-Tetramethylpiperidine-N-oxide are replaced by the equivalentamount of 2,2,6,6-Tetramethylpiperidine-4-one-N-oxide, yielding acompound of formula

EXAMPLE 3 Preparation of a Compound of Formula

A stirred mixture of 0.5 g (3.2 mmol) TEMPO, 1.14 g (6.4 mmol) of2-(4-ethyl-phenoxymethyl)-oxirane, 0.0118 g (0.032 mmol) oftetrabutylammoniumiodide and 0.62 g (4.8 mmol) of t-butylhydroperoxid(70% aqueous solution) is brought to 60° C. The temperature ismaintained at 60° C. for 4 hours until all of the TEMPO has reacted. Thereaction mixture is cooled down to 25° C. and stirred with 20 g of a 10%aqueous Na₂SO₃ solution until the disappearance of excesst-butylhydroperoxide. The aqueous phase is then separated and washedwith ethylbenzene. The combined organic phases are passed through a plugof silica gel, washed with brine, dried over MgSO₄, filtered and thesolvent distilled off on a rotary-evaporator, yielding 0.9 g of acolorless oil. Quantitative HPLC-analysis reveals aproduct-concentration of 65% w/w, corresponding to an overall yield of54.8%. ¹H-NMR (CDCl₃), δ (ppm; 2-(4-Ethyl-phenoxymethyl)-oxirane notshown): 0.63 (broad s, 3H), 1.01-1.56 (m, 15H), 1.45 (d, J=8 Hz, 3H),2.75-2.76 (m, 1H), 2.89-2.91 (m, 1H), 3.34-3.36 (m, 1H), 3.95-3.99 (m,1H), 4.17-4.21 (m, 1H), 4.73 (q, J=8 Hz, 1H), 6.84-6.88 (m, 2H),7.21-7.26 (m, 2H).

EXAMPLE 4 Preparation of the Compound of Formula

To a stirred mixture of 5 g (32 mmol) TEMPO, 39.1 g (320 mmol) ofphenetole and 0.12 g (0.32 mmol) of tetrabutylammoniumiodide, 12.37 g(96 mmol) of t-butylhydroperoxid (70% aqueous solution) are added at 60°C. within 60 minutes. The temperature is maintained at 60° C. for 21hours until all TEMPO has reacted. The reaction mixture is cooled downto 25° C. and stirred with 121 g of a 10% aqueous Na₂SO₃ solution untilthe disappearance of excess t-butylhydroperoxide. The aqueous phase isthen separated and washed with cyclohexane. The combined organic phasesare washed with brine, dried over MgSO₄, filtered. and the solvent isdistilled off on a rotary-evaporator. The crude product is purified byflash-chromatography (silica gel, Hexane/Ethylacetate 9/1), yielding 4.6g (51.8% of theory) of a slightly yellow oil. Analysis required forC₁₇H₂₇NO₂ (277.41): C, 73.61%, H, 9.81%, N, 5.05%; found: C, 73.15%, H,9.89%, N, 4.95%. ¹H-NMR (CDCl₃), δ (ppm): 1.13 (s, 3H), 1.16 (s, 3H),1.19 (s, 6H), 1.30-1.69 (m, 6H), 1.47 (d, J=8 Hz, 3H), 5.58 (q, J=8 Hz,1H), 6.92-6.96 (m, 1H), 7.01-7.03 (m, 2H), 7.24-7.28 (m, 2H).

EXAMPLE 5 Preparation of

To a stirred mixture of 50 mmol4-propoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 41.1 g (500 mmol) ofcyclohexene and 0.18 g (0.5 mmol) of tetrabutylammoniumiodide, 7.4 g (58mmol) of t-butylhydroperoxid (70% aqueous solution) are added at 55° C.within 30 minutes. The reaction mixture is cooled down to 25° C. andstirred with 63 g of an aqueous 20% Na₂SO₃ solution until thedisappearance of excess t-butylhydroperoxide. The aqueous phase is thenseparated and washed with cyclohexane. The combined organic phases arepassed through a plug of silica gel and washed with brine, dried overMgSO₄, filtered and the solvent distilled off on a rotary-evaporator.The crude product is purified by distillation, yielding the titleproduct.

EXAMPLE 6 Preparation of

by Hydrogenation of the Product of Example 5

A mixture of 4 mmol) of the product of Example 5 and 0.2 g Pd oncharcoal (10%) in 10 ml of methanol is hydrogenated at 25° C. and 4 barof hydrogen. Filtration and evaporation of the solvent yields the titleproduct as a slightly orange oil.

EXAMPLE 7 Preparation of the Compound of the Formula

To a stirred mixture of 5.5 g (35 mmol) TEMPO, 10.5 g (70 mmol) ofphenylacetic acid methyl ester and 0.13 g (0.35 mmol) oftetrabutylammoniumiodide, 6.75 g (52.5 mmol) of t-butylhydroperoxid (70%aqueous solution) are added at 60° C. within 25 minutes. The temperatureis maintained at 60° C. for 46 hours. The reaction mixture is cooleddown to 25° C. and stirred with 66 g of a 10% aqueous Na₂SO₃ solutionuntil the disappearance of excess t-butylhydroperoxide. The aqueousphase is then separated and washed with ethylbenzene. The combinedorganic phases are washed with brine, dried over MgSO₄, filtered and thesolvent distilled off on a rotary-evaporator. The crude product ispurified by flash-chromatography (silica gel, hexane:ethylacetate 9:1),yielding 6 g (56% of theory) of the title product as a white crystallinesolid, mp 85° C.-87° C. Analysis required for C₁₈H₂₇NO₃ (305.42): C,70.79%, H, 8.91%, N, 4.59%; found: C, 70.60%, H, 9.13%, N, 4.53%. ¹H-NMR(CDCl₃), δ (ppm): 0.72 (s, 3H), 1.07 (s, 3H), 1.14 (s, 3H), 1.23 (s,3H), 1.28-1.58 (m, 6H), 3.65 (s, 3H), 5.21 (s, 1H), 7.27-7.35 (m, 3H),7.43-7.45 (d-like, 2H).

EXAMPLE 8 Preparation of the Compound of the Formula

To a stirred mixture of 6.8 g (32 mmol) of2,6-diethyl-2,3,6-trimethyl-piperidin-4-one-N-oxide, 34 g (320 mmol) ofethylbenzene and 0.12 g (0.32 mmol) of tetrabutylammoniumiodide, 6.2 g(48 mmol) of t-butylhydroperoxid (70% aqueous solution) are added at 60°C. within 30 minutes. The temperature is maintained at 60° C. for 13hours, after which another 6.2 g of t-butylhydroperoxid and 0.12 g oftetrabutylammoniumiodide are added. The temperature is maintained at 60°C. for another 24 hours, cooled down to 25° C. and stirred with 120 g ofa 10% aqueous Na₂SO₃ solution until the disappearance of excesst-butylhydroperoxide. The aqueous phase is then separated and washedwith ethylbenzene. The combined organic phases are washed with brine,dried over MgSO₄, filtered and the solvent distilled off on arotary-evaporator. The crude product is purified by flash-chromatography(silica gel, hexane:Ethylacetate 9:1), yielding the title product as ayellow oil. Analysis required for C₂₀H₃₁NO₂ (317.48): C, 75.67%, H,9.84%, N, 4.41%; found: C, 74.01%, H, 9.76%, N, 4.30%. ¹H-NMR (CDCl₃), δ(ppm, O—CH only): 4.83 (p-like, 1H).

EXAMPLE 9 Preparation of the Compound of the Formula

To a stirred mixture of 6.4 g (25 mmol) of3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undecane-N-oxide, 8.9g (50 mmol) of 2-(4-ethyl-phenoxymethyl)-oxirane and 0.09 g (0.25 mmol)of tetrabutylammoniumiodide, 3.4 g (37.5 mmol) of t-butylhydroperoxid(70% aqueous solution) are added at 60° C. within 30 minutes. Thetemperature is maintained at 60° C. for 17.6 hours. The reaction mixtureis cooled down to 25° C. and stirred with 47 g of an aqueous 10% Na₂SO₃solution until the disappearance of excess t-butylhydroperoxide. Theaqueous phase is then separated and washed with cyclohexane. Thecombined organic phases are washed with brine, dried over MgSO₄,filtered and the solvent distilled off on a rotary-evaporator, yielding12.2 g of a brownish oil partially crystallizing at low temperature. Thetitle product is obtained as an off-white solid, mp 106° C.-110° C.Analysis required for C₂₅H₃₉NO₅ (433.59): C, 69.25%, H, 9.07%, N, 3.23%;found: C, 68.24%, H, 9.04%, N, 2.87%. ¹H-NMR (CDCl₃), δ (ppm): 0.63 (brs, 3H), 0.93 (br s, 3H), 0.95 (br s, 3H), 1.14 (br s, 3H), 1.30 (br s,6H), 1.45-1.48 (m, 4H), 1.53-1.60 (m, 1H), 2.05-2.09 (d-like, 1H),2.16-2.20 (d-like, 1H), 2.75-2.76 (m, 1H), 2.89-2.91 (m, 1H), 3.34-3.36(m, 1H), 3.45 (s, 4H), 3.94-3.99 (m, 1H), 4.18-4.21 (m, 1H), 4.74 (q,J=8 Hz, 1H), 6.84-6.87 (d-like, 2H), 7.22-7.25 (d-like, 2H).

EXAMPLE 10 Preparation of the Compound of the Formula

A stirred mixture of 1.42 g (2.5 mmol) ofN,N′-dibutyl-6-chloro-N,N′-bis-(2,2,6,6-tetramethyl-piperidin-4-yl-N-oxide)-[1,3,5]-triazine-2,4-diamine,4.2 g (50 mmol) cyclohexane, 0.018 g (0.05 mmol)tetrabutylammoniumiodide and 1.93 g (15 mmol) t-butylhydroperoxid (70%aqueous solution) is brought to 68° C. The temperature is maintained at68° C. for 22 hours. The reaction mixture is cooled down to 25° C. andstirred with 18.9 g of an aqueous 10% Na₂SO₃ solution until thedisappearance of excess t-butylhydroperoxide. The aqueous phase is thenseparated and washed with cyclohexane. The combined organic phases arewashed with brine, dried over MgSO₄, filtered and the solvent distilledoff on a rotary-evaporator, yielding 1.1 g g of a reddish solid.Purification by flash-chromatography (silica gel, hexane:ethylacetate9:1) yields the title product as a white solid, mp 86° C.-90° C.Analysis required for C₄₁H₇₄ClN₇O₂ (732.55): C, 67.23%, H, 10.18%, Cl,4.84%, N, 13.38%; found: C, 67.16%, H, 10.08%, Cl, 4.91%, N, 12.86%.¹H-NMR (CDCl₃), δ (ppm): 0.88-0.96 (m, 6H), 1.05-1.4 (m, 42H), 1.45-1.60(m, 6H), 1.63-1.80 (m, 8H), 2.0-2.1 (m, 4H), 3.25-3.35 (m, 4H),3.55-3.65 (m, 2H), 4.9-5.1 (m, 2H).

EXAMPLE 11 Preparation of the Compound of the Formula

To a stirred mixture of 8 g (35 mmol) of propionicacid-2,2,6,6-tetramethylpiperidin-4-yl-N-oxide ester, 29.5 g (350 mmol)cyclohexane and 0.13 g (0.35 mmol) of tetrabutylammoniumiodide, 13.5 g(105 mmol) of t-butylhydroperoxid (70% aqueous solution) are added at60° C. within 20 minutes. The temperature is maintained at 60° C. for2.8 hours. The reaction mixture is cooled down to 25° C. and stirredwith 132 g of an aqueous 10% Na₂SO₃ solution until the disappearance ofexcess t-butylhydroperoxide. The aqueous phase is then separated andwashed with cyclohexane. The combined organic phases are washed withbrine, dried over MgSO₄, filtered and the solvent distilled off on arotary-evaporator, yielding 10 g of a reddish oil. Purification byflash-chromatography (silica gel, hexane:ethylacetate 9:1) yields thetitle product as a yellowish oil. Analysis required for C₁₈H₃₃NO₃(311.47): C, 69.41%, H, 10.68%, N, 4.50%; found: C, 69.32%, H, 10.57%,N, 4.40%. ¹H-NMR (CDCl₃), δ (ppm): 1.09 (t, J=8 Hz, 3H), 1.10-1.26 (m,17H), 1.52-1.57 (m, 3H), 1.74-1.84 (m, 4H), 2.03-2.05 (m, 2H), 2.28 (q,J=8 Hz, 2H), 3.56-3.62 (m, 1H), 4.98-5.06 (m, 1H).

EXAMPLE 12 Preparation of the Compound

To a stirred mixture of 8.95 g (30 mmol)8,10-diethyl-3,3,7,8,10-pentamethyl-1,5-dioxa-9-aza-spiro[5.5]undecane-N-oxide,24.6 g (300 mmol) cyclohexene and 0.11 g (0.3 mmol)tetrabutylammoniumiodide are added at 65° C. within 20 minutes 5.8 g (45mmol) t-butylhydroperoxid (70% aqueous solution). The temperature ismaintained at 65° C. for 15 minutes until all of the N-oxide hasreacted. The reaction mixture is cooled down to 25° C. and stirred with57 g of an aqueous 10% Na₂SO₃ solution until the disappearance of excesst-butylhydroperoxide. The aqueous phase is then separated and washedwith cyclohexane. The combined organic phases are washed with brine,dried over MgSO₄, filtered and the solvent distilled off on arotary-evaporator, yielding 10.5 g (92% of theory) of a slightly orangeoil. Purification by Flash-Chromatography (silica gel,Hexane/Ethylacetate 8/2) affords 9.7 g (85% of theory) the titlecompound as a viscous, colourless oil. Analysis required for C₂₃H₄₁NO₃(379.58): C, 72.78%, H, 10.89%, N, 3.69%; found: C, 72.61%, H, 10.65%,N, 3.66%.

EXAMPLE 13 Preparation of the Compound

To a stirred mixture of 9.1 g (30 mmol)8,10-Diethyl-3,3,7,8,10-pentamethyl-1,5-dioxa-9-aza-spiro[5.5]undecane-N-oxide,31.9 g (300 mmol) Ethylbenzene and 0.11 g (0.3 mmol)Tetrabutylammoniumiodide are added at 60° C. within 25 minutes 5.8 g (45mmol) t-Butylhydroperoxid (70% aqueous solution). The temperature ismaintained at 65° C. for 15 minutes until all of the N-oxide hasreacted. The reaction mixture is cooled down to 25° C. and stirred with57 g of an aqueous 10% Na₂SO₃ solution until the disappearance of excesst-Butylhydroperoxide. The aqueous phase is then separated and washedwith Ethylbenzene. The combined organic phases are washed with Brine,dried over MgSO₄, filtered and the solvent distilled off on arotary-evaporator, yielding 12.4 g (102% of theory) of a slightly yellowoil. Purification by Flash-Chromatography (silica gel,Hexane/Ethylacetate 9.5/0.5) affords 10 g (82.6% of theory) of the titlecompound as a viscous, colourless oil. Analysis required for C₂₅H₄₁NO₃(403.61): C, 74.40%, H, 10.24%, N, 3.47%; found: C, 74.29%, H, 10.47%,N, 3.36%.

EXAMPLE 14

Preparation of the compound of Example 1 with the catalyst Bu₄Nlgenerated in situ from Bu₄NCl/Nal; yield determination by HPLC.

To a stirred mixture of 0.5 g (3.2 mmol)2,2,6,6-tetramethylpiperidine-N-oxide (TEMPO), 3.8 g (35.6 mmol)ethylbenzene, 0.0092 g (0.032 mmol) tetrabutylammoniumchloride and0.0048 g (0.032 mmol) sodium iodide dissolved in 1 ml water are added at50° C. 0.62 g (4.8 mmol) t-butylhydroperoxid (70% aqueous solution). Thetemperature is maintained at 50° C. for 80 minutes, after which a sampleis withdrawn and analyzed by quantitative HPLC. The yield is 78%.

EXAMPLE 15

Preparation of the compound of Example 12 using immobilized oniumiodide. This allows the catalyst be filtered off after the reaction.

To a stirred mixture of 8.95 g (30 mmol)8,10-diethyl-3,3,7,8,10-pentamethyl-1,5-dioxa-9-aza-spiro[5.5]undecane-N-oxide,24.6 g (300 mmol) cyclohexene and 0.3 g (0.3 mmol)tributylmethylammonium iodide bound to polystyrene (1 meq iodide/g) areadded at 70° C. within 35 minutes 5.8 g (45 mmol) t-butylhydroperoxid(70% aqueous solution). The temperature is maintained at 70° C. for 18.5hours until all of the nitroxide has reacted. The reaction mixture iscooled down to 25° C. and the catalyst filtered off. The filtrate isstirred with 57 g of an aqueous 10% Na₂SO₃ solution until thedisappearance of excess t-butylhydroperoxide. The aqueous phase is thenseparated and washed with cyclohexane. The combined organic phases arewashed with brine, dried over MgSO₄, filtered and the solvent distilledoff on a rotary-evaporator, yielding 10.7 g (94% of theory) of the titleproduct as a slightly orange oil.

EXAMPLE 16 Preparation of the Compound of Example 9

To a stirred mixture of 0.769 g (3 mmol)3,3,8,8,10,10-hexamethyl-1,5-dioxa-9-aza-spiro[5.5]undecane-N-oxide, 1.6g (9 mmol, 3 eq) 2-(4-ethyl-phenoxymethyl)-oxirane, 0.046 g (0.3 mmol,0.1 eq) biphenyl (internal standard) and 0.03 mmol (0.01 eq) oniumiodide are added at 60° C. 0.579 g (4.5 mmol, 1.5 eq)t-butylhydroperoxid (70% aqueous solution). The temperature ismaintained at 60° C. Samples are withdrawn and analyzed by quantitativeHPLC.

Using Bu₄Nl as onium iodide yields 82% of theory after 22 h (nitroxideconversion: 97%). Good results are also achieved when the amount of2-(4-ethyl-phenoxymethyl)-oxirane is reduced to 2, 1.5 or 1 eq.; or whenusing 1 eq. of 2-(4-ethyl-phenoxymethyl)-oxirane, the catalyst isreplaced by the equivalent amount of Ph₄Pl or Oct₃MeNl, or the amount ofBu₄Nl is increased to 0.15 mmol (0.05 eq.).

EXAMPLE 17 Preparation of the Compound

To a stirred mixture of 0.829 g (3 mmol) benzoicacid-2,2,6,6-tetramethyl-piperidin-4-yl-N-oxid ester, 2.53 g (30 mmol,10 eq) cyclohexane, 0.046 g (0.3 mmol, 0.1 eq) biphenyl (internalstandard) and 0.03 mmol (0.01 eq) onium iodide are added at 60° C. 0.579g (4.5 mmol, 1.5 eq) t-butylhydroperoxid (70% aqueous solution). Thetemperature is maintained constant. Samples are withdrawn after 22 h andanalyzed by quantitative HPLC. Results are given in the tables below:TABLE Yield and nitroxide conversion after 22 h reaction at varioustemperatures Reaction Product yield Nitroxide Catalyst Temperature [%]conversion [%] Bu₄NI 60° C. 33 38 Oct₃MeNI 60° C. 31 35 Bu₄NI 70° C. 4348 Bu₄NI 80° C. 46 52

Good results are also achieved when the amount onium iodide catalyst orthe amount of tert.butyl hydroperoxide is doubled. TABLE Product yieldand nitroxide conversion after 22 h reaction at 80° C. and using 9 mmol(3 eq.) of tert.butyl hydroperoxide Product yield Nitroxide conversionCatalyst [%] [%] Bu₄NI 63 69 Oct₄NI 59 67 Hexadecyl₄NI 59 68 Dodecyl₄NI58 67 Hex₄NI 58 68 Octadecyl₂Me₂NI 57 64 HexadecylBzMe₂NI 57 63Tetradecyl₂Me₂NI 56 63 Oct₃PrNI 56 65 OctBzMe₂NI 56 63 Oct₃MeNI 54 63HexadecylPyI 54 59 Oct₂Me₂NI 53 62 OctMe₃NI 52 57 Et₄N 38 42 Oct₂MeSI 1217 Ph₄PI 74 88 Ph₃iPrPI 71 87 Ph₃EtPI 63 74 Ph₃HexPI 61 71 Bu₄PI 61 68Bu₃HexadecylPI 61 68 Oct₄PI 58 66 Ph₃MePI 57 65 Ph₂Me₂PI 51 56 Et₄PI 4650 PhMe₃PI 39 44 Ph₃(CH₂CO₂Me)PI 36 35 Ph₃BzPI 34 40Abbreviations:Me methyl, Et ethyl, Pr n-propyl, iPr iso-propyl, Bu n-butyl, Hexn-hexyl, Oct n-octyl, Ph phenyl, Bz benzyl, Py 1-pyridinium

Using a wide variety of catalysts, the present process effectivelyconverts the N-oxide into the desired product, yielding only low levelsof by-products.

EXAMPLE 18 Preparation of the Compound of Example 17 Using Ph₄Pl asCatalyst

To a stirred mixture of 8.3 g (30 mmol) benzoicacid-2,2,6,6-tetramethyl-piperidin-4-yl-N-oxid ester, 25.4 g (300 mmol)cyclohexane and 0.14 g (0.3 mmol) tetraphenylphosphonium iodide areadded at 80° C. within 30 minutes 11.6 g (90 mmol) t-butylhydroperoxid(70% aqueous solution). The temperature is maintained at 80° C. for 19.3hours. The reaction mixture is cooled down to 25° C. and stirred withaqueous 10% Na₂SO₃ solution until the disappearance of excesst-butylhydroperoxide. The aqueous phase is then separated and washedwith cyclohexane. The combined organic phases are washed with brine,dried over MgSO₄, filtered and the solvent distilled off on arotary-evaporator, yielding 9 g of a red oil. Purification byflash-chromatography (silica gel, hexane/ethylacetate 9/1) affords 6.8 g(63% of theory) of the product as a viscous, colorless oil. Analysisrequired for C₂₂H₃₃NO₃ (359.51): C, 73.50%, H, 9.25%, N, 3.90%; found:C, 72.68%, H, 9.39%, N, 3.85%.

EXAMPLE 19 Preparation of the Compound

To a stirred mixture of 7.7 g (45 mmol) triacetoneamine-N-oxide, 37.3 g(450 mmol) cyclohexene and 0.17 g (0.45 mmol) tetrabutylammonium iodideare added at 60° C. within 1 hour 17.4 g (135 mmol) t-butylhydroperoxid(70% aqueous solution). The temperature is maintained at 60° C. for 21.7hours. After further addition of catalyst (0.24 g, 0.45 mmoltrioctylmethylammonium iodide) and t-butylhydroperoxide (17.4 g, 135mmol) the temperature is maintained another 24 hours. The reactionmixture is then cooled down to 25° C. and stirred with aqueous 10%Na₂SO₃ solution until the disappearance of excess t-butylhydroperoxide.The aqueous phase is separated and washed with cyclohexane. The combinedorganic phases are washed with brine, dried over MgSO₄, filtered and thesolvent distilled off on a rotary-evaporator, yielding 11.7 g of anorange oil. Purification by flash-chromatography (silica gel,hexane/ethylacetate 9/1) affords the title product as a colorless oil.Analysis required for C₁₅H₂₅NO₂ (251.37): C, 71.67%, H, 10.02%, N,5.57%; found: C, 71.33%, H, 10.03%, N, 5.78%.

EXAMPLE 20 Preparation of the Compound

To a stirred mixture of 5 g (32 mmol) TEMPO, 52.5 g (320 mmol)2-Phenylethylacetate and 0.12 g (0.32 mmol) Tetrabutylammoniumiodide areadded at 60° C. within 25 minutes 12.37 g (96 mmol) t-Butylhydroperoxid(70% aqueous solution). The temperature is maintained at 60° C. for18.67 hours until all of the TEMPO has reacted. The reaction mixture iscooled down to 25° C. and stirred with 121 g of an aqueous 10% Na₂SO₃solution until the disappearance of excess t-Butylhydroperoxide. Theaqueous phase is then separated and washed with Ethylbenzene. Thecombined organic phases are washed with Brine, dried over MgSO₄,filtered and the solvent distilled off on a rotary-evaporator. The crudeproduct is purified by flash-chromatography (silica gel,Hexane/Ethylacetate 9/1), yielding the title product as a colorless oil.Analysis for C₁₉H₂₉NO₃ (319.45): C, 71.44%, H, 9.15%, N, 4.38%; found:C, 71.36%, H, 9.20%, N, 4.21%. ¹H-NMR (CDCl₁₃), δ (ppm): 0.66 (broad s,3H), 1.08-1.60 (m, 15H), 1.95 (s, 3H), 4.23-4.30 (m, 1H), 4.57-4.61 (m,1H), 4.91 (t, J=8 Hz, 1H), 7.28-7.37 (m, 5H).

EXAMPLE 21 Preparation of the Compound

To a stirred mixture of 7.8 g (50 mmol) TEMPO, 41.1 g (500 mmol)Cyclohexene and 0.18 g (0.5 mmol) Tetrabutylammoniumiodide are added at55° C. within 30 minutes 7.4 g (58 mmol) t-Butylhydroperoxid (70%aqueous solution). The reaction mixture is cooled down to 25° C. andstirred with 63 g of an aqueous 20% Na₂SO₃ solution until thedisappearance of excess t-Butylhydroperoxide. The aqueous phase is thenseparated and washed with Cyclohexane. The combined organic phases arepassed through a plug of silica gel and washed with Brine, dried overMgSO₄, filtered and the solvent distilled off on a rotary-evaporator.The crude product is purified by distillation, yielding 8 g (67.4% oftheory) of an orange oil (bp 62° C.-65° C./0.04 mbar). Analysis requiredfor C₁₅H₂₇NO (237.39): C, 75.90%, H, 11.46%, N, 5.90%; found: C, 75.69%,H, 11.99%, N 5.75%. ¹H-NMR (CDCl₃), δ (ppm): 1.13-2.07 (m, 24H), 4.24(br s, 1H), 5.77-5.81 (m, 1H), 5.91-5.95 (m, 1H).

EXAMPLE 22 Hydrogenation of the Product of Example 21

A mixture of 0.95 g (4 mmol)1-(Cyclohex-2-enyloxy)-2,2,6,6-tetramethyl-piperidine and 0.2 g Pd oncharcoal (10%) in 10 ml Methanol is hydrogenated at 25° C. and 4 barHydrogen. Filtration and evaporation of the solvent yields the titleproduct as a slightly orange oil. Analysis for C₁₅H₂₉NO (239.40): C,75.26%, H, 12.21%, N, 5.85%; found: C, 74.53%, H, 12.07%, N, 5.90%.¹H-NMR (CDCl₃), δ (ppm): 1.12-1.39 (m, 19H), 1.40-1.65 (m, 7H), 1.74 (brs, 1H), 2.04 (br s, 1H), 3.58 (m, 1H).

EXAMPLE 23 Hydrogenation of the Crude Product of Example 21

A mixture of the crude product from example 21 (10.87 g, 91.6% oftheory) and 2.4 g Pd on charcoal (10%) in 120 ml Methanol ishydrogenated as described in example 22. Filtration and evaporation ofthe solvent yields 6.8 g of a slightly yellow oil. Analysis required forC₁₅H₂₉NO (239.40): C, 75.26%, H, 12.21%, N, 5.85%; found: C, 74.53%, H,12.07%, N 5.90%. ¹H-NMR (CDCl₃), δ (ppm): 1.12-1.39 (m, 19H), 1.40-1.65(m, 7H), 1.74 (br s, 1H), 2.04 (br s, 1H), 3.58 (m, 1H).

EXAMPLE 24 Preparation of the Compound

To a stirred mixture of 7.3 g (32 mmol) Propionicacid-2,2,6,6-tetramethylpiperidin-4-yl-N-oxide ester, 26.3 g (320 mmol)Cyclohexene and 0.12 g (0.32 mmol) Tetrabutylammoniumiodide are added at55° C. within 25 minutes 6.2 g (48 mmol) t-Butylhydroperoxid (70%aqueous solution). The temperature is maintained at 55° C. for 5 minutesuntil all of the TEMPO has reacted. The reaction mixture is cooled downto 25° C. and stirred with 61 g of an aqueous 10% Na₂SO₃ solution untilthe disappearance of excess t-Butylhydroperoxide. The aqueous phase isthen separated and washed with Cyclohexane. The combined organic phasesare passed through a plug of silica gel and washed with Brine, driedover MgSO₄, filtered and the solvent distilled off on arotary-evaporator, yielding 8.7 g (87.9% of theory) of the above productas a slightly orange oil. Analysis required for C₁₈H₃₁NO₃ (309.45): C,69.87%, H, 10.10%, N, 4.53%; found: C, 69.36%, H, 10.03%, N, 4.45%.¹H-NMR (CDCl₃), δ (ppm): 1.12 (t, J=8 Hz, 3H), 1.20-1.26 (m, 12H),1.52-1.58 (m, 4H), 1.73-2.1 (m, 6H), 2.29 (q, J=8 Hz, 2H), 4.23 (m, 1H),5.05 (m, 1H), 5.79-5.82 (m, 1H), 5.90-5.94 (m, 1H).

EXAMPLE 25 Hydrogenation of the Product of Example 24

A mixture of CG40-1201 (1 g, 3.19 mmol) and 0.17 g Pd on charcoal (10%)in 30 ml Hexane is hydrogenated as described in example 6. Filtrationand evaporation of the solvent yields 0.9 g (90.6% of theory) of aslightly yellow oil. Analysis required for C₁₈H33NO₃ (311.47): C,69.41%, H, 10.68%, N, 4.50%; found: C, 69.20%, H, 10.76%, N, 4.42%.¹H-NMR (CDCl₃), δ (ppm): 1.09 (t, J=8 Hz, 3H), 1.10-1.26 (m, 17H),1.52-1.57 (m, 3H), 1.74-1.84 (m, 4H), 2.03-2.05 (m, 2H), 2.28 (q, J=8Hz, 2H), 3.56-3.62 (m, 1H), 4.98-5.06 (m, 1H).

EXAMPLE 26 Preparation of the Compound

To a stirred mixture of 14.2 g (25 mmol) ofN,N′-Dibutyl-6-chloro-N,N′-bis-(2,2,6,6-tetramethyl-piperidin-4-yl-N-oxide)-[1,3,5]-triazine-2,4-diamine,41 g (500 mmol) Cyclohexene and 0.18 g (0.5 mmol)Tetrabutylammoniumiodide are added at 57° C. within 30 minutes 9.7 g (75mmol) t-Butylhydroperoxid (70% aqueous solution). The temperature ismaintained at 57° C. for 5 minutes until all of the TEMPO has reacted.The reaction mixture is cooled down to 25° C. and stirred with 63 g ofan aqueous 10% Na₂SO₃ solution until the disappearance of excesst-Butylhydroperoxide. The aqueous phase is then separated and washedwith Cyclohexane. The combined organic phases are washed with Brine,dried over MgSO₄, filtered and the solvent distilled off on arotary-evaporator, yielding 14.5 g (79.6% of theory) of a slightlyyellow solid. Crystallization from Acetone/Hexane yields 12.2 g (67%) ofa white solid, mp 83° C.-87° C. Analysis required for C₄₁H₇₀ClN₇O₂(728.51): C, 67.60%, H, 9.69%, Cl, 4.87%, N, 13.46%; found: C, 67.27%,H, 9.63%, Cl, 4.97%, N, 13.34%. ¹H-NMR (CDCl₃), δ (ppm): 0.89-0.96 (m,6H), 1.22-1.32 (m, 26H), 1.49-1.56 (m, 12H), 1.73-1.78 (m, 8H),1.89-2.04 (m, 6H), 3.31-3.32 (m, 4H), 4.24-4.26 (m, 2H), 4.99-5.06 (m,2H), 5.80-5.83 (m, 2H), 5.92-6.02 (m, 2H).

1. Process for the preparation of an amine ether of a stericallyhindered amine by reacting a corresponding sterically hindered aminoxidewith an aliphatic hydrocarbon compound, wherein the reaction is carriedout in the presence of an organic hydroperoxide and an iodide: 2.Process of claim 1 for the preparation of an amine ether of a stericallyhindered amine by reacting a corresponding sterically hindered aminoxidewith a hydrocarbon compound, wherein the reaction is carried out in thepresence of an organic hydroperoxide and a catalytic amount of aniodide.
 3. Process of claim 1, wherein the amine ether is of the formulaA

wherein a is 1 or 2; when a is 1, E′ is E when a is 2, E′ is L; E isC₁-C₃₆ alkyl; C₃-C₁₈ alkenyl; C₂-C₁₈ alkinyl; C₅-C₁₈ cycloalkyl; C₅-C₁₈cycloalkenyl; a radical of a saturated or unsaturated aliphatic bicyclicor tricyclic hydrocarbon of 7 to 12 carbon atoms; C₂-C₇alkyl orC₃-C₇alkenyl substituted by halogen, C₁-C₈alkoxy or phenoxy;C₄-C₁₂heterocycloalkyl; C₄-C₁₂heterocycloalkenyl; C₇-C₁₅ aralkyl orC₄-C₁₂heteroaralkyl, each of which is unsubstituted or substituted byC₁-C₄ alkyl or phenyl; or E is a radical of formula (VII) or (VIII)

wherein Ar is C₆-C₁₀aryl or C₅-C₉heteroaryl; X is phenyl, naphthyl orbiphenyl, which is substituted by 1, 2, 3 or 4 D and optionally furthersubstituted by NO₂, halogen, amino, hydroxy, cyano, carboxy,C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylamino or di(C₁-C₄alkyl)amino; Dis a group

a group C(O)-G₁₃ or a group C(O)-G₉-C(O)-G₁₃; G₁ and G₂, independentlyof each other, are hydrogen, halogen, NO₂, cyano, —CONR₅R₆, —(R₉)COOR₄,13 C(O)—R₇, —OR₈, —SR₈, —NHR₈, —N(R₁₈)₂, carbamoyl,di(C₁-C₁₈alkyl)carbamoyl, —C(═NR₅)(NHR₆), C₁-C₁₈alkyl; C₃-C₁₈alkenyl;C₃-C₁₈alkinyl, C₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl orC₂-C₁₂heterocycloalkyl; C₁-C₁₈alkyl or C₃-C₁₈alkenyl or C₃-C₁₈alkinyl orC₇-C₉phenylalkyl, C₃-C₁₂cycloalkyl or C₂-C₁₂heterocycloalkyl substitutedby OH, halogen, NO₂, amino, cyano, carboxy, COOR₂₁, C(O)—R₂₂,C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylamino or di(C₁-C₄alkyl)amino or agroup —O—C(O)—R₇; C₂-C₁₈alkyl which is interrupted by at least one Oatom and/or NR₅ group; or are C₆-C₁₀aryl; or phenyl or naphthyl whichare substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, halogen,cyano, hydroxy, carboxy, COOR₂₁, C(O)—R₂₂, C₁-C₄alkylamino ordi(C₁-C₄alkyl)amino; or G₁ and G₂ together with the linking carbon atomform a C₃-C₁₂cycloalkyl radical; G₅ and G₆ are independently of eachother H or CH₃; G₉ is C₁-C₁₂alkylene or a direct bond; G₁₃ isC₁-C₁₈alkyl; G₁₄ is C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, an acyl radical of analiphatic or unsaturated aliphatic carboxylic or carbamic acidcontaining 2 to 18 carbon atoms, an acyl radical of a cycloaliphaticcarboxylic or carbamic acid containing 7 to 12 carbon atoms, or acylradical of an aromatic acid containing 7 to 15 carbon atoms; G₅₅ is H,CH₃ or phenyl; G₆₆ is —CN or a group of the formula —COOR₄ or —CONR₅R₆or —CH₂—O-G₁₄; L is alkylene of 1 to 18 carbon atoms, cycloalkylene of 5to 8 carbon atoms, cycloalkenylene of 5 to 8 carbon atoms, alkenylene of3 to 18 carbon atoms, alkylene of 1 to 12 carbon atoms substituted byphenyl or by phenyl substituted by alkyl of 1 to 4 carbon atoms; or isalkylene of 4 to 18 carbon atoms interrupted by COO and/or phenylene; T′is tertiary C₄-C₁₈alkyl or phenyl, each of which are unsubstituted orsubstituted by halogen, OH, COOR₂₁ or C(O)—R₂₂; or T′ isC₅-C₁₂cycloalkyl; C₅-C₁₂cycloalkyl which is interrupted by at least oneO or —NR₁₈—; a polycyclic alkyl radical having 7-18 carbon atoms, or thesame radical which is interrupted by at least one O or —NR₁₈—; or T′ is—C(G₁)(G₂)-T″; or C₁-C₁₈alkyl or C₅-C₁₂cycloalkyl substituted by

T″ is hydrogen, halogen, NO₂, cyano, or is a monovalent organic radicalcomprising 1-50 carbon atoms; or T″ and T′ together form a divalentorganic linking group completing, together with the hindered aminenitrogen atom and the quaternary carbon atom substituted by G₁ and G₂,an optionally substituted five- or six-membered ring structure; and R₄is hydrogen, C₁-C₁₈alkyl, phenyl, an alkali metal cation or atetraalkylammonium cation; R₅ and R₆ are hydrogen, C₁-C₁₈alkyl,C₂-C₁₈alkyl which is substituted by hydroxy or, taken together, form aC₂-C₁₂alkylene bridge or a C₂-C₁₂-alkylene bridge interrupted by Oor/and NR₁₈; R₇ is hydrogen, C₁-C₁₈alkyl or C₆-C₁₀aryl; R₈ is hydrogen,C₁-C₁₈alkyl or C₂-C₁₈hydroxyalkyl; R₉ is C₁-C₁₂alkylene or a directbond; R₁₈ is C₁-C₁₈alkyl or phenyl, which are unsubstituted orsubstituted by halogen, OH, COOR₂₁ or C(O)—R₂₂; R₂₁ is hydrogen, aalkali metal atom or C₁-C₁₈alkyl; and R₂₂ is C₁-C₁₈alkyl; the aminoxideis of formula B

and the hydrocarbon is of formula IV or VE-H  (IV)H-L-H  (V) wherein E, G₁, G₂, L, T and T′ are as defined for formula A.4. Process according to claim 1, wherein the organic hydroperoxide is aperoxoalcohol containing 3-18 carbon atoms.
 5. Process according toclaim 1, wherein 1 to 100 moles of the hydrocarbon, 1 to 20 moles oforganic hydroperoxide, and 0.001 mmoles to 0.5 moles of iodide catalystare used per mole of aminoxide.
 6. Process according to claim 1, whichis carried out in the absence of copper or a copper compound.
 7. Processaccording to claim 1, wherein the hydrocarbon is used in excess andserves both as reactant and as solvent for the reaction and/or wherein afurther inert organic or inorganic solvent is used.
 8. Process accordingto claim 1, wherein the reaction is carried out in the presence of aphase transfer catalyst.
 9. Process according to claim 8, wherein thecatalyst is selected from alkaline or alkaline earth metal iodides,ammonium iodides and phosphonium iodides.
 10. Process according to claim3, wherein in the formulae A and B T and T′ together are an organiclinking group containing 2-500 carbon atoms and 0-200 hetero atomsselected from oxygen, phosphorus, sulfur, silicon, halogen and nitrogenas tertiary nitrogen, and forming, together with the carbon atoms it isdirectly connected to and the nitrogen atom, an optionally substituted,5-, 6 or 7-membered cyclic ring structure.
 11. Process according toclaim 1, wherein the aliphatic hydrocarbon compound contains anethylenic double bond, and the product is subsequently hydrogenated. 12.(canceled)
 13. A compound of the formula a, b c or d


14. (canceled)